US7217773B2 - Method for producing polyisobutene - Google Patents

Method for producing polyisobutene Download PDF

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US7217773B2
US7217773B2 US10/542,928 US54292805A US7217773B2 US 7217773 B2 US7217773 B2 US 7217773B2 US 54292805 A US54292805 A US 54292805A US 7217773 B2 US7217773 B2 US 7217773B2
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alkanol
carbon atoms
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US20060063901A1 (en
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Hans Peter Rath
Thomas Perner
Helmut Mach
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C08F10/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C08F110/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
    • C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for preparing polyisobutene having a content of terminal vinylidene groups of at least 75 mol %.
  • terminal vinylidene groups or terminal double bonds are those double bonds whose position in the polyisobutene macromolecule is described by the general formula
  • R is a polyisobutenyl radical.
  • the type and the proportion of the double bonds present in the polyisobutene can be determined with the aid of 1 H or 13 C NMR spectroscopy.
  • Such highly reactive polyisobutenes are used as intermediates for preparing additives for fuels and lubricants, as described, for example, in DE-A 27 02 604.
  • the highest reactivity is exhibited by the terminal vinylidene groups having 2-methyl substitution, whereas neopentyl substitution or double bonds disposed further toward the center of the macromolecule, depending on their position in the macromolecule, exhibit only slight reactivity, if any, in the customary functionalization reactions.
  • the proportion of terminal vinylidene groups in the molecule is therefore the most important quality criterion for this type of polyisobutene.
  • U.S. Pat. No. 5,286,823 describes a process for preparing highly reactive polyisobutenes by cationic polymerization of isobutene in the presence of boron trifluoride and secondary alcohols having from 3 to 20 carbon atoms and/or ethers having from 2 to 20 carbon atoms.
  • WO 93/10063 discloses boron trifluoride etherate complexes in which the ether has at least one tertiary carbon atom bonded to the ether oxygen atom.
  • the complexes serve to polymerize olefins, in particular isobutene, to polymers having a high content of vinylidene groups.
  • EP-A 1 026 175 describes the preparation of isobutene polymers having at least 80 mol % of molecules with terminal vinylidene structure using complex catalysts of boron trifluoride, ether and alcohol and/or water in certain amounts.
  • the achievable molecular weight of the polyisobutene depends decisively on the relative amount of the boron trifluoride complex catalyst based on the olefin monomers used. Larger amounts of catalyst achieve lower molecular weights and vice versa. The amount of boron trifluoride required in the preparation of low molecular weight polyisobutenes constitutes a considerable cost factor. The disposal of the catalyst deactivation products extracted into an aqueous phase also entails a considerable wastewater burden. U.S. Pat. No. 6,407,186 and WO02/40553 therefore recommend processes for removing and recycling the catalyst.
  • this object is achieved by a process for preparing polyisobutene having a content of terminal vinylidene double bonds of at least 75 mol % by polymerizing isobutene or isobutenic hydrocarbon mixtures in the liquid phase in the presence of a boron trifluoride complex catalyst of the composition (BF 3 ) a .L 1 b .L 2 c .L 3 d where
  • Useful feedstocks (isobutene feedstocks) for the process according to the invention are both pure isobutene and isobutenic hydrocarbon mixtures, for example low-butadiene C 4 raffinates from crackers or C 4 cuts of isobutane dehydrogenation having isobutene contents of more than 40% by weight. It is also possible to use inert solvents such as saturated hydrocarbons, for example pentane, hexane, isooctane or halogenated hydrocarbons such as dichlormethane or trichloromethane.
  • inert solvents such as saturated hydrocarbons, for example pentane, hexane, isooctane or halogenated hydrocarbons such as dichlormethane or trichloromethane.
  • the catalysts used in the process according to the invention are boron trifluoride complexes having at least one starter selected from water, primary C 1 –C 5 -alkanols and secondary C 3 –C 5 -alkanols, at least one regulator selected from aldehydes and ketones and optionally at least one solubilizer selected from ethers having at least 5 carbon atoms, secondary alkanols having at least 6 carbon atoms, primary alkanols having at least 6 carbon atoms and tertiary alkanols.
  • starter and regulator influences the polymerization activity of the boron trifluoride in such a way that the polymerization firstly results in a low molecular weight polyisobutene and secondly the isomerization activity of the boron trifluoride with regard to the isomerization of terminal double bonds to double bonds disposed in the interior of the polyisobutene molecule and having no or only little reactivity is reduced.
  • starter refers to the isomerization of terminal double bonds to double bonds disposed in the interior of the polyisobutene molecule and having no or only little reactivity is reduced.
  • the starters L 1 are compounds having a hydrogen atom without significant steric hindrance bonded to an oxygen atom. They are referred to a “starters” because their active hydrogen atom is incorporated at the beginning of the growing polyisobutene chain.
  • suitable L 1 are water, methanol, ethanol, 2-propanol and/or 1-propanol. Among these, greatest preference is given to methanol.
  • the regulators L 2 are aldehydes and/or ketones which typically have from 1 to 20, preferably from 2 to 10 carbon atoms, and in which functional groups other than the carbonyl group are preferably absent.
  • suitable L 2 are formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, acetone, methyl ethyl ketone and diethyl ketone.
  • acetone acetone.
  • the solubilizers L 3 have a solubilizing action and increase the solubility of the catalyst complex in the starting material.
  • These are ethers having at least 5 carbon atoms or long-chain and/or sterically hindered alcohols which offer screening against the entry of isobutene molecules. Preference is given to using dialkyl ethers having from 5 to 20 carbon atoms, a secondary alkanol having from 6 to 20 carbon atoms, a primary alkanol having from 6 to 20 carbon atoms and/or a tertiary C 4 –C 20 -alkanol. When primary alkanols are used, these preferably have a ⁇ -branching, i.e.
  • Suitable representatives are, for example, selected from methyl tert-butyl ether, di-n-butyl ether, di-n-hexyl ether, dioctyl ether, 2-ethylhexanol, 2-propylheptanol, the oxo alcohols of dimeric, trimeric and tetrameric propylene, and dimeric and trimeric butene, linear 1-alcohols (which are obtainable, for example, by the Alfol® process), as long as they are liquid under the reaction conditions, such as n-hexanol or n-octanol, and tert-butanol. Among these, greatest preference is given to 2-ethylhexanol.
  • the boron trifluoride complex catalysts can be preactivated before they are used or generated in situ in the polymerization reactor, as described in EP-A 628 575.
  • the raw material used for preparing the boron trifluoride complex catalysts is advantageously the gaseous boron trifluoride, which may be technical-grade boron trifluoride still containing small amounts of sulfur dioxide and SiF 4 (purity: 96.5% by weight), although preference is given to using highly pure boron trifluoride (purity: 99.5% by weight). Particular preference is given to using silicon tetrafluoride-free boron trifluoride for the catalyst preparation.
  • conventional reactors such as tubular reactors, tube bundle reactors or stirred tanks may be used.
  • the polymerization is preferably effected in a loop reactor, i.e. a tubular or tube bundle reactor having constant circulation of the reaction mixture, and the ratio of feed to circulation F/C can generally be varied within the range from 1:5 to 1:500, preferably within the range from 1:10 to 1:200 v/v.
  • the polymerization is advantageously effected at temperatures below 0° C., preferably at temperatures in the range from 0 to ⁇ 40° C., in particular in the range from 0 to ⁇ 30° C. and more preferably in the range from ⁇ 10 to ⁇ 30° C.
  • the polymerization is carried out at a pressure in the range from 0.5 to 20 bar (absolute).
  • the choice of the pressure range is governed primarily by the process engineering conditions. For instance, in the case of stirred tanks, it is recommended to work with evaporative cooling and therefore under autogenous pressure, i.e. subatmospheric pressure, whereas circulation reactors (loop reactors) work better at superatmospheric pressure. At the same time, pressure and turbulence accelerate the metering in of boron trifluoride, so that preference is given to this reactor type. However, the choice of the pressure is generally unimportant to the result of the polymerization reaction.
  • the residence time of the isobutene to be polymerized in the reactor is in the range from 1 to 120 minutes, preferably in the range from 5 to 60 minutes.
  • the reaction effluent is advantageously conducted into a medium which deactivates the polymerization catalyst and in this way terminates the polymerization.
  • a medium which deactivates the polymerization catalyst for example, water, alcohols, ethers, acetonitrile, ammonia, amines or aqueous solutions of mineral bases such as alkali metal and alkaline earth metal hydroxide solutions, solutions of carbonates of these metals, and the like can be used.
  • Preference is given to terminating with water at a temperature of from 20 to 40° C., for example in the form of scrubbing under pressure. The temperature of the water used depends on the desired mixing temperature at which the phase separation takes place.
  • the polymerization mixture is optionally subjected to one or more extractions to remove residues of catalyst, typically methanol, or water scrubbing.
  • catalyst typically methanol, or water scrubbing.
  • water scrubbing apart from the catalyst, hydrogen fluoride formed in the course of the polymerization is also removed.
  • unconverted isobutene, solvent and volatile isobutene oligomers are removed distillatively.
  • the bottoms are freed of residues of solvent and monomers, for example using thin-film evaporators, falling-film evaporators, annular-gap evaporators or Sambay evaporators, optionally with the addition of steam or nitrogen gas.
  • isobutene When pure isobutene is used as the starting material, it can be recycled into the polymerization, in the same way as isobutene oligomers and solvents.
  • isobutenic C 4 cuts When isobutenic C 4 cuts are used, the unconverted isobutene and the remaining C 4 hydrocarbons are generally not recycled, but rather fed to other uses, for example the preparation of low molecular weight polyisobutene or of methyl t-butyl ether.
  • Volatile fluorine-containing by-products such as sec-butyl and tert-butyl fluoride can be removed from the polyisobutene together with the other hydrocarbons and separated from these hydrocarbons distillatively or extractively.
  • the process according to the invention enables highly reactive polyisobutenes to be prepared both from pure isobutene and from isobutenic hydrocarbon mixtures.
  • the process according to the invention allows number-average molecular weights in the range from 500 to 50000 dalton, preferably from 500 to 5000 dalton, in particular from 500 to 2500 dalton, at a content of terminal double bonds of at least 75 mol %, preferably at least 78 mol %, in particular at least 80 mol %.
  • the polyisobutenes obtained are characterized by a narrow molecular weight distribution. They preferably have a dispersity M w /M n in the range from 1.3 to 5, in particular from 1.3 to 2.
  • a circulation reactor was used which consisted of a Teflon hose having an internal diameter of 6 mm and a length of 7.1 m through which 1000 l/h of reactor contents were circulated by a gear pump. Tube and pump had a capacity of 200 ml. Teflon hose and pump head were disposed in a cold bath at a temperature of ⁇ 25° C.
  • the feed used was a hydrocarbon stream of the following composition (in % by weight) which was obtained by selective butadiene hydrogenation of a C 4 cut stemming from a steam cracker operated with naphtha:
  • the feed rate was 700 g/h.
  • the feed was dried over 3 ⁇ molecular sieves at 5° C. to a water content of less than 3 ppm, precooled to ⁇ 25° C. and fed to the circulation reactor.
  • BF 3 and complexing agent were fed in the amounts specified in the table which follows to the suction side of the circulation pump directly into the circulation reactor.
  • the effluent was quenched in a mixing pump immediately after leaving the circulation reactor with aliquots of water, the aqueous phase was removed and the organic phase was dried over 3 ⁇ molecular sieves. After low boilers and isobutene oligomers had been removed at 220° C. and 2 mbar, the molecular weight M W , M N and the vinylidene group contents of the residue obtained were determined.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US10/542,928 2003-01-24 2004-01-23 Method for producing polyisobutene Expired - Lifetime US7217773B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10303212A DE10303212A1 (de) 2003-01-24 2003-01-24 Verfahren zur Herstellung von Polyisobuten
DE10303212.6 2003-01-24
PCT/EP2004/000569 WO2004065432A1 (de) 2003-01-24 2004-01-23 Verfahren zur herstellung von polyisobuten

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EP (1) EP1590381B1 (de)
JP (1) JP4124788B2 (de)
KR (1) KR101008921B1 (de)
CN (1) CN100338104C (de)
AT (1) ATE328913T1 (de)
DE (2) DE10303212A1 (de)
TW (1) TW200422303A (de)
WO (1) WO2004065432A1 (de)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013062758A1 (en) 2011-10-26 2013-05-02 Tpc Group Llc Polyisobutylene prepared at high velocity and circulation rate
EP2604635A1 (de) 2011-12-16 2013-06-19 The University of Massachusetts System zur Polymerisierungseinleitung und Verfahren zur Herstellung hochreaktiver funktionaler Olefinpolymere
RU2485139C1 (ru) * 2012-04-05 2013-06-20 Открытое акционерное общество "ЭКТОС-Волга" Способ получения высокореактивного низкомолекулярного полиизобутилена
EP2778181A1 (de) 2013-03-12 2014-09-17 University of Massachusetts System zur Polymerisierungseinleitung und Verfahren zur Herstellung hochreaktiver funktionaler Olefinpolymere
EP2860206A1 (de) 2013-10-11 2015-04-15 University of Massachusetts System zur Polymerisierungseinleitung und Verfahren zur Herstellung hochreaktiver funktionaler Olefinpolymere
US9074026B2 (en) 2011-10-26 2015-07-07 Tpc Group Llc Polyisobutylene prepared with low diluent content reaction medium
US9309339B2 (en) 2011-10-26 2016-04-12 Tpc Group Llc Mid-range vinylidene content, high viscosity polyisobutylene polymers
EP3098246A1 (de) 2015-05-13 2016-11-30 University of Massachusetts System zur polymerisierungseinleitung und verfahren zur herstellung hochreaktiver polybutene
US10047174B1 (en) 2017-06-28 2018-08-14 Infineum International Limited Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10167352B1 (en) 2017-06-28 2019-01-01 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10174138B1 (en) 2018-01-25 2019-01-08 University Of Massachusetts Method for forming highly reactive olefin functional polymers
US20200270377A1 (en) * 2015-12-17 2020-08-27 Jxtg Nippon Oil & Energy Corporation Method for producing butene polymer
US10829573B1 (en) 2019-05-21 2020-11-10 Infineum International Limited Method for forming highly reactive olefin functional polymers

Families Citing this family (8)

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DE102005049236A1 (de) * 2005-10-14 2007-04-19 Basf Ag Verfahren zur Herstellung von Polyisobuten
DE102007061224A1 (de) 2007-01-10 2008-07-17 Basf Se Verfahren zur Verringerung der Klebrigkeit von Polymer-Formkörpern
EP2768871B1 (de) * 2011-10-21 2015-09-30 Basf Se Verfahren zur herstellung von isobutenhomo- oder -copolymeren
US8853336B2 (en) 2012-02-17 2014-10-07 Basf Se Boron trifluoride-catalyst complex and process for preparing high-reactivity isobutene homopolymers
SG10201606559UA (en) 2012-02-17 2016-09-29 Basf Se Boron trifluoride catalyst complex and method for producing highly reactive isobutene homopolymers
KR101628897B1 (ko) * 2014-06-18 2016-06-09 대림산업 주식회사 노르말 프로판올을 포함한 촉매를 이용한 폴리부텐의 제조방법
WO2023198616A1 (en) * 2022-04-14 2023-10-19 Basf Se Process for manufacturing of polyisobutene succinic anhydrides
WO2023198589A1 (en) * 2022-04-14 2023-10-19 Basf Se Process for manufacturing of polyisobutene succinic anhydrides

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9266980B2 (en) 2011-10-26 2016-02-23 Tpc Group Llc Polyisobutylene prepared at high velocity and circulation rate
WO2013062758A1 (en) 2011-10-26 2013-05-02 Tpc Group Llc Polyisobutylene prepared at high velocity and circulation rate
US9309339B2 (en) 2011-10-26 2016-04-12 Tpc Group Llc Mid-range vinylidene content, high viscosity polyisobutylene polymers
US8946361B2 (en) 2011-10-26 2015-02-03 Tpc Group Llc Polyisobutylene prepared at high velocity and circulation rate
US9074026B2 (en) 2011-10-26 2015-07-07 Tpc Group Llc Polyisobutylene prepared with low diluent content reaction medium
WO2013090764A1 (en) 2011-12-16 2013-06-20 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
EP2604635A1 (de) 2011-12-16 2013-06-19 The University of Massachusetts System zur Polymerisierungseinleitung und Verfahren zur Herstellung hochreaktiver funktionaler Olefinpolymere
US9034998B2 (en) 2011-12-16 2015-05-19 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
RU2485139C1 (ru) * 2012-04-05 2013-06-20 Открытое акционерное общество "ЭКТОС-Волга" Способ получения высокореактивного низкомолекулярного полиизобутилена
EP2778181A1 (de) 2013-03-12 2014-09-17 University of Massachusetts System zur Polymerisierungseinleitung und Verfahren zur Herstellung hochreaktiver funktionaler Olefinpolymere
US9156924B2 (en) 2013-03-12 2015-10-13 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
EP2860206A1 (de) 2013-10-11 2015-04-15 University of Massachusetts System zur Polymerisierungseinleitung und Verfahren zur Herstellung hochreaktiver funktionaler Olefinpolymere
US9631038B2 (en) 2013-10-11 2017-04-25 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
EP3098246A1 (de) 2015-05-13 2016-11-30 University of Massachusetts System zur polymerisierungseinleitung und verfahren zur herstellung hochreaktiver polybutene
US9771442B2 (en) 2015-05-13 2017-09-26 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US20200270377A1 (en) * 2015-12-17 2020-08-27 Jxtg Nippon Oil & Energy Corporation Method for producing butene polymer
US11008409B2 (en) * 2015-12-17 2021-05-18 Eneos Corporation Method for producing butene polymer
US10047174B1 (en) 2017-06-28 2018-08-14 Infineum International Limited Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10167352B1 (en) 2017-06-28 2019-01-01 University Of Massachusetts Polymerization initiating system and method to produce highly reactive olefin functional polymers
US10174138B1 (en) 2018-01-25 2019-01-08 University Of Massachusetts Method for forming highly reactive olefin functional polymers
US10829573B1 (en) 2019-05-21 2020-11-10 Infineum International Limited Method for forming highly reactive olefin functional polymers

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ATE328913T1 (de) 2006-06-15
CN1742026A (zh) 2006-03-01
CN100338104C (zh) 2007-09-19
DE502004000719D1 (de) 2006-07-20
US20060063901A1 (en) 2006-03-23
EP1590381B1 (de) 2006-06-07
JP4124788B2 (ja) 2008-07-23
JP2006513313A (ja) 2006-04-20
KR20050100627A (ko) 2005-10-19
EP1590381A1 (de) 2005-11-02
WO2004065432A1 (de) 2004-08-05
DE10303212A1 (de) 2004-08-05
TW200422303A (en) 2004-11-01

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